Documente Academic
Documente Profesional
Documente Cultură
by:
SHAILENDRA KR.
Classes at: -
Meq. Approach
Matter
NO
Hetrogeneous Mixture
Is it uniform throughout?
YES
Homogeneous
NO
YES
Homogeneous Mixture (Solution)
Pure substace
NO
YES
Compound
Element
PHYSICAL CHEMISTRY
Page No.: 1
Chemical Equations
A chemical changes involves a reorganization of the atoms in one or more substances. For Example, when the methane (CH4) in natural gas combines with oxygen (O2) in the air and burns, carbon dioxide (CO2) and Water (H2O) Are formed. This process is represented by a chemical equation with reactants (here methane and oxygen) on the left side of and the products (carbon dioxide and water) on the right side : CH4 + O2 Reactants CO2 + 2H2O Products
Notice that the atoms have been reorganized. Bonds have been broken, and new ones formed it is important to recognize that in a chemical reaction atoms are neither created nor destroyed. All atoms present in the reactants must be accounted for among the products. In other words, there must be the same number of each type of atom on the product side and on the reactant side of the arrow. Making sure that this rule is obeyed is called balancing a chemical equation for a reaction. CH4 + O2 Reactant 1C 4H 2O CO2 + 2H2O Product 1C 4H 2O Page No.: 2
PHYSICAL CHEMISTRY
Products
CO2 (g) + 2H2O (g) 1 molecule CO2 + 2 molecules H2O 1 mole CO2 molecules + 2 mole H2O molecules 6.022 1023 CO2 molecules +2(6.022 1023)H2O molecules 44 g CO2 + 2(18 g) H2O 80 g product
PHYSICAL CHEMISTRY
Page No.: 3
MOL CONCEPT
! A mol (Symbol mol) is defined as the quantity of given substance that contains as many molecules or formula units as the no of atoms in exactly 12 gm of C12. The number of atoms in a 12 gm sample of C12 is called Avogadros number (NA). Recent measurement of this number gives the value 6.0221367 1023, which to three significant figures is 6.02 1023. ! A mol Avogadros no (6.02 1023) of molecules or formula units. ! A mol of a substance contains Avogadros no (6.02 1023) of molecules (or formula units). The term mol, like a Dozen. A Dozen equals 12 eggs , a gross of Pencil equal 144 Pencil. Mol is also known as chemist dozen. ! In using the term mol for ionic substance, we mean the number of formula units of the substances. For example, a mol of sodium carbonate Na2CO3 is a quantity containing 6.02 1023 Na2CO3 units. But each formula unit of Na2CO3 contains two Na+ ions and one CO32 ions. The SI unit for an amount of matter is called the mole. In the same way that the amount of certain objects (such as apples or eggs) is often expressed in terms of multiples or fractions of a unit we call dozen, the amounts of the building blocks of matter (such as protons, electrons, atoms or molecules) are expressed in terms of multiples or fractions of a unit we call mole, or just mol for short. Thus, if you are familiar with expressions such as two dozen eggs or half a dozen apples, you will easily see the similarity with expressions such as 3 mol sulphuric acid, half a mol of copper atoms and 0.001 mol photons. Of course, everyone knows that the unit we call dozen is associated with the number 12. But mole is defined as the amount of matter which contains the same number of elementary particles of the matter in question as there are atoms in 0.012 kg of the carbon isotope 12 C.
Molar mass
If the relative atomic mass of an atom (or the relative molar mass of a molecule, or the relative formula mass of a salt, as the case may be) is expressed in grams, this gives rise to a quantity known as the molar mass of the substance in question. Equal numbers of moles of different substances always contain the same number of elementary particles. Just as half a dozen eggs is always 6 eggs and half a dozen onions is always 6 onions, half a mole of hydrogen gas is always equal to 3.012 x 1023 molecules of H2. Similarly, we know that half a mole of gold is always equal to 3.012 x 1023 atoms of Au. To convert a given number of moles of a substance to the corresponding mass in grams, multiply the relative molar mass (or relative atomic mass for an monatomic element) by the number of moles, and express the result in grams.
PHYSICAL CHEMISTRY
Page No.: 4
Avogadros law
The constancy of the molar volume of gases is explained in terms of Avogadros Law, formulated in by 1811 by Amedeo Avogadro. Equal volumes of all gases, measured at the same temperature and pressure, will contain the same number of molecules. CH4 N2 CO2 SO2
These balloons hold 1.0 litre of gas at 25C and 1.0 atm each balloons contains .041 mole 22 of gas or 2.5 10 molecules.
Molecular Weight
Weight of one mole molecule in gram is known as Molecular Weight of molecule or weight of one molecule in amu. is known as molecular weight of molecule. For Example:- Molecular weight of CO2 is 44. It means weight of one molecule CO2 is 44 amu or weight of one mole molecule CO2 is 44 g. Weight of one mole molecule CO2 is 44 gm. or, Weight of NA molecule CO2 is 44 gm. 24 Weight of one molecule of CO2 is 44 / NA gm. or 44 amu. (1/NA = 1 amu. = 1 dalton = 1.66 10 gm)
Atomic Weight
Weight of one mole atom in gram is known as atomic Weight of atom or weight of one atom in amu. is known as atomic weight of atom. For Example:- atomic weight of He is 4. It means weight of one atom He is 4 amu or weight of one mole atom He is 4 g. Weight of one mole atom He is 4 gm. or, Weight of NA atom He is 4 gm. 24 Weight of one atom of He is 4 / NA gm. or 4 amu. (1/NA = 1 amu. = 1 dalton = 1.66 10 gm) Page No.: 5 PHYSICAL CHEMISTRY By: Shailendra Kumar
Specific Gravity (Sp. Gr.) of a substance is the ratio of its density to the density of water, both at the same temperature. Specific gravities are dimensionless numbers. D substance Sp. Gr. = D water The density of water is 1.000 g/mL at 3.98C, the temperature at which the density of water is greater However, variations in the density of water with changes in temperature are small enough that we may use 1.00 g/mL up to 25C.
Vapour Density
It is defined as mass of one mole vapour with respect to mass of one mole H2. mass of one mole vapour molecular weight Vapour Density = = mass of one mole H2 2 Molecular weight = 2 Vapour Density
Relative Density
It is defined as density of one substance respect to density of other substance. Q. Ans. Calculate relative density of Cl2 with respect to air. (Molecular weight of air is 29 g/mole) Vapour Density of Cl2 Relative density of Cl2 wrt air = Vapour Density of air = Q. Vapour Density of Cl2 2 Molecular weight of Cl2 71 = = = 2.45 Vapour Density of air 2 Molecular weight of air 29
105 mL of pure water at 4C saturated with NH3 gas yeilded a solution of density 0.9 g mL1 and containing 30% NH3 by mass. Find out the volume of NH3 solution resulting and the volume of NH3 gas at 4C and 775 mm of Hg which was used to saturate water. [Ans: 166.67 mL solution, 59.03 litre pure NH3]
PHYSICAL CHEMISTRY
Page No.: 6
! When using the term mol, it is important to specify the formula of the unit to avoid any misunderstanding. ! 1 mol oxygen (Confusing) 1 mol oxygen may be (a) 1 mol oxygen molecule (b) 1 mol oxygen atom. The molar mass of a substance is the mass of one mol substance. C12 has molar mass of exactly 12 gm/mol, by definition. Mole can be defined in three terms : 1. Mole in terms of number 2. Mole in terms of mass 3. Mole in terms of volume. 1. MOLE IN TERMS OF NUMBER: Mole of an unit of chemists to count atoms, molecules, ions, electrons, protons, neutrons, Chemical bond etc. and one mole of any thing is equal to 6.0221023 pieces or particle of that thing. e.g., One mole of Na = 6.0221023 atom of Na One mole of H2O = 6.0221023 molecule of H2O One mole of CO23 = 6.0221023 ions of CO23. No. of mole = No. of particle Mol NA Particle For ion No. of atom Mol NA atom No of mole = For electron No. of molecule Mol NA molecule = 1 mol He atom = 2 mol oxygen atom = 2 mol CO2 molecule = 1 mol SO42 ion = 2 mol Na+ ion No of mole = No. of electron Mol NA electron No. of ion Mol NA ion
" No of particle may be atom, molecule, ion, electron, proton, neutron, photon etc.
For atom No of mole = For molecule No of mole =
= 1 6.022 1023 He atom = 2 6.0221023 oxygen atom = 26.0221023 CO2 molcule = 16.0221023 SO42 ion = 26.0221023 Na+ ion
" 1 mol C6H12O6 = 1 mol C6H12O6 molecule = 16.0221023 C6H12O6 molecule " 1 mol SO42
2 mol Na+
2. MOLE IN TERMS OF MASS : One gram atom of an element or one gram molecule of a substance or one gram ion of an ion is known as one mole of that element or substance or ion respectively. e.g., (i) One gram atom Na = One mole Na
PHYSICAL CHEMISTRY
Page No.: 7
= 23 g Na = 6.022 1023 atoms of Na. (ii) One gram molecule H2O = One mole H2O = 18 g H2O = 6.022 1023 molecule of H2O. (iii) One gram ion of CO23 = One mole CO23 = 60 g CO23 = 6.0221023 ions of CO23. 3. MOLE IN TERMS OF VOLUME OR STANDARD MOLAR VOLUME OR MOLAR VOLUME : One mole of any gas contains 22.4 liters at N.T.P or S.T.P. (0C & 760 m.m of Hg), the volume is called molar volume of standard molar volume of oftenly called gram molecular volume. e.g., (i) One mole NH3 = 22.4 litres NH3 at N.T.P. (Molar volume or gram molecular volume) = One gram molecule NH3 = 17 g NH3 = 6.0221023 molecules of NH3. (ii) One mole of He = 22.4 litre He at N.T.P. (Molar volume or gram atomic volume) = One gram atom He = 4 g He = 6.0221023 atoms of He. (iii) One mole of Hydrogen = 22.4 litres hydrogen at N.T.P. (Molar volume or gram molecular volume) = 2 g hydrogen = 6.0221023 molecules of hydrogen = 26.0221023 atoms of hydrogen.
PHYSICAL CHEMISTRY
! Concept 1 :
===== =
Mol is a unit like Dozen. 1 Dozen = 12 unit. 1 mol = NA = 6.022 1023 unit Avogadro number Ex. 1.
Calculate number of Dozen in 24 particle of any substance. No of particles 12 particle Dozen 24 particle Dozen = 12 particle = 2 DOZEN. [Ans : 2]
Solution : No of DOZEN =
Ex.2.
Calculate number of mol of 6.022 1024 particle of any substance. No of particles 6.022 1023(NA) particle /mol 6.022 1024 particle mol 6.022 1024 particle
Solution : No of mol =
= 10 [Ans : 10]
Note : (i) Consider 1 mol molecule C6H12O6 (consist of 6 mol of C atom, 12 mol of atom & 6 mol of O atom) Total mol of atom = 24. (ii) Consider x mol of molecule C6H12O6 = x mol C6H12O6 = (Generally written) (consist of 6x mol of C atom, 12x mol of H atom & 6x mol of O atom) Total mol of atom = 24x Ex.3. : Calculate number of oxygen atom present in 9.8 gm H2SO4. No of mol of H2SO4 =
Solution :
= 9.8/9.8 = 0.1
0.1 mol of H2SO4 i.e., 0.1 4 mol oxygen atom. No. of atom = 0.4 NA oxygen atom.
! Concept 2:
(a) Consider 1 molecule C6H12O6. (Consist of 6 atom of C, 12 atom of H and 6 atom of O)
(b)
! Concept 3 :
Consider 1 mol of C6H12O6 1 Mol of C6H12O6 is confusing word.
PHYSICAL CHEMISTRY
Page No.: 9
No of molecule in 1 mol molecule C6H12O6. No of molecule = 1 NA molecule C6H12O6. Analogous example : 2 DOZEN egg = 2 12 eggs.
! Concept 4 :
Molecular weight of C6H12O6 is 180. It means weight of one mol molecule C6H12O6 is 180 gm. Ex. Solution: Calculate weight of 1 molecule in the term of (a) gm (b) amu ( Atomic Mass Unit) weight of 6.023 1023 molecule C6H12O6 is 180 gm.
(a) weight of 1 molecule C6H12O6 is 180 1.66 1024 gm. (b) weight of 1 molecule C6H12O6 is 180 amu. [ Ans : (a) 180 1.66 1024 gm (b) 180 amu ] Note : (i) Atomic weight of He is 4. It means weight of 1 mol He atom is 4 gm. Hence weight of atom He can be calculate in the term of gm and amu. Weight of one atom He = 1.66 1023 4 gm Weight of one atom He = 4 amu (ii) Weight of 1 molecule CO2 is 44 amu. Weight of 1 molecule H2SO4 is 98 amu. Weight if 10 molecule C6H12O6 is 180 amu.
! Concept 5 :
EX.1 : Calculate percentage of Carbon atom in C6H12O6.
% of C =
PHYSICAL CHEMISTRY
180
6.022 1023
1 molecule C6H12O6
CONSIST 6 12 amu 12 amu 6 6 amu
C atom
H atom
O atom
No of C atom 12 100
Mol wt of C6H12O6 Page No.: 10
Conclusion : % of particular atom No. of particular atom in molecule Molecular weight of substance No. of particular atom in substance. Note : Minimum molecular wt of substance means molecule consist contain 1 atom s atom. (Which is described in problem) EX.2 : Solution : Calculate minimum mot-wt of insulin. If it contains 3.4% s atom. Minimum molecular weight of insulin means insulin contain ! Atom s atom. ( Infact insulin molecule consist 6 atoms) % of S =
1 32
Minimum molecular weight
100
3200
3.4
[Ans :
3200
3.4
2)
3)
4)
5)
6)
7)
PHYSICAL CHEMISTRY
Page No.: 11
PHYSICAL CHEMISTRY
Page No.: 12
DILUTION
To save time and space in the laboratory routinely used solutions are often purchased or prepared in concentrated form called stock solution. water is then added to achieve the molarity desired for particular solution this process is called dilution. For example :the common acids are purchased as concentrated solutions and diluted as needed.
Dilution Calculation
200 ml of ...... M C6H12O6 Weight of C6H12O6 = 50 103 180 gm During dilution weight of solute Mol. weight of solute No of mol of solute No of milli mol of solute
Remains constant ,, ,, ,, ,, ,, ,,
We can say No of millimol before dilution = No of millimol after dilution M1V1 = M2V2 In another words if we dilution x times then for keep millimol of solute constant we must divide molarity of solution by a factor x. xX
No of millimol = MXV(M1) x
. .
M 1/V
Page No.: 13
PHYSICAL CHEMISTRY
No of Meq.
= N XV(M1) x
. .
Constant (during dilution) Conclusion :- During Dilution, weight of solute, no of solute, no of millimole of solute, no of equivalent of solute or no of meq of solute remains constant [Q] what volume of 16 M sulphuric acid must be used to prepare 1.5 liter of a 0.10 M H2SO4? Solution :- Millimol before dilution = Millimole after dilution 16 V(L) = 1.5 0.10 V(L) = 0.15/16 = 9.4 103L or 9.4 ml solution. Thus to make 1.5 L of 0.10 M H2SO4 using 16 M H2SO4, we must take 9.4 ml of the concentrated acid and dilution with water to 1.5 L. The correct way to do this is to add the 9.4 ml of acid to about 1.0 L of water and then dilute to 1.5 L by adding more water.
PRACTICE PROBLEM [Q] 1. 15.8 gm Na2S2O3 dissolved in water and make 250 mL solution, 25 mL the solution is diluted 10 times. Calculate molarity of final solution. Ans:- 0.04 M [Q] 2. Calculate pH of 102 M HCl when it is diluted (a) 10 times (b) 102 times (c) 103 times (d) 104 times Ans :- (a) 3 (b) 4 (c) 5 (d) 6 [Q] 3. Calculate change in pH when 5 103 M H2SO4 is diluted (a) 10 times (b) 102 times (c) 103 times (d) 104 times Ans :- (a) 3 (b) 4 (c) 5 (d) 6 [Q] 4. 18 g glucose dissolved in water and make 250 mL solution, 25 mL the solution is diluted 10 times. 25 mL of this diluted solution add into 500 mL volumetric flask and filled water to the mark, 50 mL of this solution added into 250 mL volumetric flask and filled water to the mark. Calculate (a) Molarity of final solution (b) weight of C6H12O6 in final solution (c) Mole of C6H12O6 in final solution (d) molecule of C6H12O6 in final solution (e) weight of C, H, and O in final solution (f) number of C, H, and O in final solution Ans :- Solved in class room [Q] 5. 15.8 g KMnO4 dissolved in water and make 250 mL solution, 25 mL the solution is diluted 10 times.25 mL of this diluted solution add into 500 mL volumetric flask and filled water to the mark, 50 mL of this solution added into 250 mL volumetric flask and filled water to the mark. Calculate (a) Molarity of final solution (b) weight of KMnO4 in final solution (c) Mole of KMnO4 in final solution (d) molecule of KMnO4 in final solution (e) weight of K, Mn, and O in final solution (f) number of K, Mn, and O in final solution Ans :- Solved in class room [Q] 6 Calculate pOH when 5 103 M Ca(OH)2 is diluted (a) 10 times (b) 102 times (c) 103 times (d) 104 times Ans :- (a) 3 (b) 4 (c) 5 (d) 6
PHYSICAL CHEMISTRY
Page No.: 14
Simple Rules For Solubility Of Salts In Water Most nitrate (NO ) salts are soluble. Most salt of Na+, K+ and NH4+ are soluble. Most chloride salt are soluble notable exceptions are AgCl, PbCl2 and Hg2Cl2. Most sulphate salts are soluble . Notable exception are BaSO4, PbSO4, and CaSO4. Most hydroxide salts are only slightly soluble. The important soluble hydroxides are NaOH, KOH and Ca(OH)2. Most sulphide (S2), Carbon ate (CO32) and phosphate (PO43) salts are only slightly soluble.
3
(Q) Using solubility rule, predict what will happen when the following pairs of solution are mixed. (a) KNO3(aq) and BaCl2(aq) (b) Na2SO4(aq) and Pb(NO3)2(aq) (c) KOH(aq) and Fe(NO3)3(aq). Solution :(a) No precipitation reaction occur (b) Precipitation of PbSO4 takes place (c) Precipitation of Fe(OH)3 takes place. Selective Precipitation Separation of cations by precipitating them by an anion one at a time, called selective precipitation. Suppose we have an aqueous solution containing the cations Ag+, Ba+2 and Fe+3. Reactivity of there cations tested with Cl1, SO42 and OH. ANION
Add NaCl
Solution of Fe+3
NaOH
Fe(OH)3 Precipitate
The process where by mixtures of ion are separated and identify is called qualitative analysis. PHYSICAL CHEMISTRY
Page No.: 15
Solubility Rule
Rule Applies t0
1 Li+, Na+, K+, NH4+
Statement
Group IA and ammonium compounds are soluble.
Exceptions
2 3 4 5 6 7 8
Acetates and nitrates are soluble. Most chlorides, bromides, and iodides are soluble. Most sulfates are soluble. Most carbonates are insoluble. Most phosphates are insoluble. Most sulfides are insoluble. Most hydroxides are insoluble
Agcl, Hg2Cl2, PbCl2, AgBr2, HgBr2, Hg2Br2, PbBr2, AgI, HgI2, Hg2I2, PbI2 CaSO4, SrSO4, BaSO4, Ag2SO4, Hg2SO4, PbSO4 Group IA carbonates, (NH4)2CO3 Group IA phosphates, (NH4)3PO4 Group IA sulfides, (NH4)2S Group IA hydroxides, Ca(OH)2, Sr(OH)2, Ba(OH)2
Formula
Cl
Name
chloride ion bromide ion iodide ion nitrate ion perchlorate ion chlorate ion hydrogen sulfate ion sulfate ion
sulfuric acid
HSO4 SO42
Consider the ionization of hydrochloric acid. Pure hydrogen chloride, HCl is a gas at room temperature and atmospheric pressure. When it dissolved in water,it reacts nearly 100% to produce a solution that contains hydrogen ions and chloride ions : H2O HCl(g) H+(aq) + Cl(aq) (to completion) Similar equations can be written for all strong acids.
PHYSICAL CHEMISTRY
Page No.: 16
Weak acid Ionize slightly (usually less than 5%) in dilute aqueous solutions many common weak acids are listed below :
Formula
F CH3COO CN NO2
Name
fluoride ion acetate ion cyanide ion nitrite ion hydrogen carbonate ion carbonate ion hydrogen sulfite ion sulfite ion dihydrogen phosphate ion hydrogen phosphate ion phosphate ion hydrogen oxalate ion oxalate ion
carbonic acid
HCO3 CO32
H2SO3
sulfurous acid
HSO3 SO32
H3PO4
phosphoric acid
(COOH)2
oxalic acid
H(COO)2 (COO)22
PHYSICAL CHEMISTRY
Page No.: 17
Titration
Acid-Base Titration
Titration is a chemical process in which the unknown strength of solution is measured by known strength of another solution. or A procedure in which one solution is added to another solution until the chemical reaction between the two solute is complete usually the concentration of one solution is known and the other is unknown.
End Point
The stage during titration at which completion of reaction indicated by an indicator known as end point. Indicator indicate completion of reaction by change of color. It gives rough result.
Equivalent Point The stage during titration at which completion of reaction indicated by Ph meter. It gives completely accurate result. At this point meq of acid is equal to meq base. Standard solution A solution of known strength is called standard solution. Standardization is a process by which one determines the concentration of solution by measuring accurately the volume of solution repaired to react with exactly known amount of primary standard. The standardized solution is then know as secondary standard. The Properties Of An Ideal Primary Standard Includes The Following: (1) (2) (3) (4) (5) (6) It must not react with or absorb the components of the atmosphere. Such as water, vapor, oxygen and carbon dioxide. It must react according to one invariable reaction. It must have high percentages purity. It should have high formula weight to minimize the effect of error in weighting. It must be soluble in the solvent of interest. It should be nontoxic. Primary standard are often costly and difficult to prepare, secondary standard are used in dayto-day work. Examples of primary standard (a) (b) Na2CO3 for acid KHP (Potassium hydrogen Phthalate) for acid Acid-base titration are an example of volumetric analyses, a technique in which one solution is used to analyze another. The solution used to carry out the analysis is called the titrant and is delivered from a device called a buret, which measures the volume accurately. The point in the titration at which enough titrant has been added to react exactly with the substance being determined is called the equivalence point of the stoichiometric point. The following requirements must be met for a titration to be successful: (1) (2) (3) (4) The concentration of the titrant must be known. Such a titrant is called a standard solution. The exact reaction between titration and substance being analyzed must be known. The stoichiometric (equivalent) point must be known. An indicator that changes color at, of very near, the stoichiometric point is often used. The point at which the indicator changes color is called the endpoint. The goal is to choose and indicator whose end point coincides with the stoichiometric point. An indicator very commonly used for acid-base titrations is phenolphthalein, which is colorless in acid and turns pink at the end point when an acid is titrated with a base The volume of titrant required to reach the stoichiometric point must be known as accurately as possible.
"
(5)
PHYSICAL CHEMISTRY
Page No.: 18